Allyl ethers

ABSTRACT

Allyl ethers or esters of aliphatic alcohols or acids wherein the aliphatic chain contains an epoxide group and at least 7 carbon atoms. The ethers and esters are useful in killing and preventing the proliferation of insects by upsetting their hormonal balance.

United States Patent [191 Chodnekar et al. June 3, 1975 ALLYL ETHERS V [75] Inventors: Madhukar Subraya Chodnekar, [2%] 1.15.8] 260/348 R Base]; Albert Pfiffner, Pfaffhausen; [58] Fntid C07d l/18 Norbert Rigassi Arlesheim; Ulrich ie 0 earc 260/348 R Schwieter, Reinach; Milos Suchy, pf ffh u n n f i l d Primary ExaminerN0rma S. Milestone Attorne A em, or FirmSamuel L. Welt; J S. [73] Ass1gnee: gojffmann-La Roche Inc., Nutley, Saxe; i 'i Gaither on [22] Filed: Aug. 23, 1973 [57] ABSTRACT [21] PP N04 390,962 Allyl ethers or esters of aliphatic alcohols or acids Related US. Application Data 4 wherein the aliphatic chain contains an epoxide group [63] continuatiommpmt of Sen 108,599, Jan 21, and at least carbon atoms. The ethers and esters are 1971 p NO, 3 7 1 309 useful 1n killing and preventing the proliferation of inv sects by upsetting their hormonal balance. [30] Foreign Application Priority Data Jan. 27, 1970 Switzerland 1104/70 1 Claim, N0 Drawings ALLYL ETHERS R is hydrogen, methyl or ethyl; and m and n are in gers of to 1;

- upset the hormone balance of pests such as insects CROSS SRELATED prevent them from growing and reproducing.

The compounds of formula I are prepared by epo This application is a continuation-in-part of applidizing a compound of formula:

m n R5 R'g cants copending application Ser. No. 108,599, filed wherein R1, R2, R'2, R3, 12,, R5, R6, R7, x, m and n2 Jan. 21, 1971, entitled Allyl Ethers and Esters, as as above.

originally filed and now U.S. Pat. No. 3,781,309. The compounds of formulaa I are also prepar through the dehydrohalogenation of a halohydrin SUMMARY OF THE INVENTION the formula:

W r frl r I C=-CH -XCCH=CR l l i CH3 R4 L I m E R5 3'2 In accordance with this invention, it has been found wherein R R R' R R R R R X, m and n a that compounds of the formula: as above, and Z is chlorine, bromine or iodine.

R R R 1 l R2 l l CH -C\:'/C [H -"CH5" C=CH CH CH C=CH X-T CI-I=--CR.

O R I R 2 h i R i h l or ethyl; R R' d R are b The compounds of formula I are further prepared drogen, methyl or ethyl; R is hydrogen or methyl; R reacting a compound of the form l P? r PR3 l I CH3 K7 1 0 2 CH2 0-: CH- CHK 0 m in R and R are hydrogen, lower alkyl, lower alkenyl, with a compound of the-formula: lower alkynyl, lower aryl or lower aryl-lower alkyl,

wherein R,, R R R R R R R m and n are as above; one of K and J is chlorine, bromine or iodine and the other is an alkali salt of the hydroxyl group; and R is individually hydrogen and R individually is hydrogen, methyl or ethyl or R and R taken together 5 form an additional carbon-carbon bond; to give a compound of the formula:

V t I.

wherein R R R R and m are as above; with a compound of the formula:

wherein R is lower alkyl, phenyl, halophenyl and loweralkoxyphenyl; and R R R R and R are as above; to give a compound of the formula:

I I ll rine and iodine. As used throughout this application, the term lower alkyl comprehends both straightchain and branched chain saturated alkyl hydrocarbon groups containing from 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, etc. The term lower alkenyl, as used herein, includes both straight and branched chain unsaturated alkenyl hydrocarbon 1 e e I I VI groups having from 2 to 6 carbon atoms, such as vinyl allyl, butenyl, pentenyl, and the like. The term lower alkynyl, as used herein, includes both straight and branched chain, acetylenic unsaturated hydrocarbon having from 2 to 6 carbon atoms such as ethynyl, propargyl, butynyl, etc.

The term lower aryl, as used throughout the application, signifies mono-nuclear, aromatic hydrocarbons O VII such as phenyl, tolyl, etc. which can be unsubstituted or substituted in one or more positions with a lower VIII alkylenedioxy, a halogen, a nitro, a lower alkyl, a lower alkoxy, a lower alkynyl, a lower alkynyloxy, a lower alkenyl or a lower alkenyloxy substituent, and polynu- 0 -III DETAILED DESCRIPTION OF THE INVENTION The term halogen or halo", as used throughout this application, when not expressly stated otherwise, includes all four halogens, i.e., bromine, chlorine, fluoclear aryl groups such as naphthyl, anthryl, phenanthryl, azulyl, etc. which may be substituted with one or more of the aforementioned groups. The preferred lower aryl group is phenyl which can be either unsubstituted or substituted with one of the aforementioned groups. The term lower aryl-lower alkyl comprehends lower aryl-lower alkyl groups wherein aryl is defined as above and the alkyl is lower alkyl. The preferred lower aryl-lower alkyl group is benzyl. The lower I aryl moiety of the lower aryl-lower alkyl group can be either unsubstituted or substituted with one of the aforementioned groups.

As used herein, the term lower alkylenedioxy designates lower alkylenedioxy groups having l4 carbon atoms such as methylene dioxy and ethylenedioxy. As used herein, the term lower alkoxy comprehends lower alkoxy groups containing from 1 to 6 carbon atoms, such as methoxy, propoxy, ethoxy, etc. The term lower alkenyloxy, as utilized herein, comprehends,lower alkenyloxy groups wherein lower alkenyl is defined as above. Among the preferred lower a1- kenyloxy groups are included vinyloxy, allyloxy, butenyloxy and pentenyloxy. The term alkynyloxy, as used herein, comprehends the lower alkynyloxy groups wherein lower alkynyl is defined as above.

The compounds of formula I are useful in the control of pests such as Ephestia Kuniella (flour moth) and Tenebrio molitor (yellow meal worm). In contrast to most of the known pest-control agents which kill, disable or repell the pests by acting as contract-poisons and feed-poisons, the compounds of formula I above prevent maturation and proliferation of these pests by interfering with their hormonal system. In insects, for example, the transformation to the imago, the laying of viable eggs and the development of laid normal eggs is disturbed. Furthermore, the sequence of generations is interrupted and the insects are indirectly killed.

The compounds of formula I above are practically non-toxic to vertebrates. The toxicity of the compounds of formula I is greater than, 1,000 mg/kg body weight. Moreover, these compounds are readily degraded and the risk of accumulation is therefore excluded. Therefore, these compounds can be used without fear of danger in the control of pests in animals; plants; foods; and textiles.

Generally, in controlling invertebrate animals, the compounds of formula I above are applied to the material to be protected, e.g., foodstuffs, feeds, textiles, plants in amounts of from about 10 to 10 gm/cm Generally, it is preferred to utilize the compounds of formula I above in a composition with a suitable inert carrier. Any conventional inert carrier can be utilized. Such a composition contains one or more compounds of formula I in a concentration from about 0.01 to about 0.5%, preferably 0.1%.

The compounds of formula I can, for example, be used in the form of emulsions, suspensions, dusting agents, solutions or aerosols. In special cases, the materials to be protected (e.g., foodstuffs, seeds, textiles and the like) can also be directly impregnated with the appropriate compound or with a solution thereof. Moreover, the compounds can also be used in a form which only releases them by the action of external influences (e.g., contact with moisture) or in the animal body itself.

The compounds of formula I above can be used as solutions suitable for spraying on the material to be protected which can be prepared by dissolving or dispersing these compounds in a solvent such as mineral oil fractions; cold tar oils; oils of vegetable or animal origins; hydrocarbons such as naphthalenes; ketones such as methyl ethyl ketone; or chlorinated hydrocarbons such as tetrachloroethylene, tetrachlorobenzene. and the like. The compounds of formula l above can also be prepared in forms suitable for dilution with water to form aqueous liquids such as, for example, emulsion concentrates, pastes or powders. The compounds of formula I above can be combined with solid carriers for making, dusting or strewing powders as, for example talc, kaolin, bentonite, calcium carbonate, calcium phosphate, etc. The compositions containing the compounds of formula I above can contain, if desired, emulsifiers, dispersing agents, wetting agents, or other active substances such as fungicides, bacteriacides, nematocides, fertilizers and the like. The materials which are to be protected act as bait for the insect. In this manner, the insect, by contacting the material impregnated with a compound of formula I above, also contacts the compound itself.

In accordance with this invention, the preferred compounds of formula I above are those where R R and R are hydrogen, lower alkyl, lower alkenyl, lower alkynyl, lower aryl, or lower aryl-lower alkyl, where the lower aryls may be unsubstituted or substituted in one or more positions with a halogen, a lower alkyl, a lower alkyloxy or a nitro substituent. Particularly preferred are compounds of formula I above where: R R and R are hydrogen, lower alkyl, lower alkenyl, lower alkynyl and lower aryl.

Among the most preferred compounds of formula I above are included:

1-(allyloxy)-4,5-epoxy- 1 ,S-dimethyl-hexane;

1-(al1y1oxy)-6,7-epoxy-3 ,7-dimethyl-2-octene;

1-(a11yloxy)-10,l l-epoxy-3,7,1 l-trimethyl-2,6-

dodecadiene;

1-(allyloxy)-10,1 1-epoxy-3,7,l l-trimethyl-2,6-

tridecadiene;

1-(a1lyloxy)- 1 0,1 l-epoxy-7-ethyl-3,l l-dimethyl-2,6-

tridecadiene;

1-[ 1-( 3 ,4-methylenedioxy-phenyl)-allyloxy]-6,7-

epoxy-3,6,7-trimethyl-2-octene;

10,1 1-epoxy-3,7, l 0,1 1-tetramethyl-2,6-

dodecadienoic acid allyl ester;

10,1 1-epoxy-3 ,7,1 1-trimethyl-2,6dodecadienoic acid allyl ester;

10,1 1-epoxy-7-ethyl-3 ,1 l-dimethyl-2,6-

tridecadienoic acid allyl ester; 6,7-epoxy-3,7-dimethyl-2-octenoic acid allyl ester; 1-(1,l-dimethyl-allyloxy)-6,7-epoxy-3,7-dimethyl-2- octene;

10,1 1-epoxy-3,7,l l-trimethyl-[(3-methyl-2,4-

pentadieny1)oxy]-2,6-dodecadiene;

10,1 1-epoxy-3 ,7 ,1 l-trimethyl-[ 3-methyl-2-penten-4- ynyl)-oxy]-2,6dodecadiene; and

10,1 1-epoxy-3,7 ,1 l-trimethyl-2,o-dodecadienoic acid 3-methyl-2-penten-4-ynyl ester.

Among the starting materials which can be utilized to prepare the compounds of formula I are included;

allyl 1,5-dimethyl-4-hexenyl ether;

allyl 3,7-dimethyl-2,6-octadienyl ether;

3,7,11-trimethyl-2,6,l0-dodecatrienoic acid allyl ester;

3,7,11-trimethyl-2,6,IO-tridecatrienoic acid allyl ester;

3,7-dimethyl-2,6-octadienoic acid allyl ester;

3 ,7-dimethyl-2,6-octadienyl 1,1-dimethyl-allyl ether;

allyl 3,7,1 1-trimethyl-2,6,10-dodecatrienyl and 3-methyl-2,4-pentadienyl dodecatrienyl ether; allyl 7-ethyI-3,l l-dimethy-l-2,6, l O-tridecatrienyl ether.

One method for preparing a compound of formula I above involves epoxidizing a compound of formula II in an inert solvent with a peracid. For this purpose, a compound of formula Il is dissolved in an inert solvent.

3,7,1 l-trimethyl-2,6,10-

etherf Any conventional inert solvent may be uzilized, with halogenated hydrocarbon solvents such as chloroform or carbon tetrachloride being preferred and methylene chloride being especially preferred. Although temperature and pressure are not critical, this reaction is preferably carried out at a temperature of from about C. to about 40C. Any conventional peracid can be utilized. Among the preferred peracids are included performic acid, peracetic acid, perbenzoic acid, perphthalic acid or pertungstic acid, with mchloroperbenzoic acid being especially preferred.

Another method for preparing a compound of formula I above involves dehydrohalogenation a compound of formula III above with a base. For this purpose, the compound of formula III is dissolved in a conventional solvent, preferably in an alkanol where X is an oxymethylene group, methanol being especially preferred, or in an ether where X is a carbonyl group, diethyl ether being especially preferred. Any conventional base can be utilized, but the alkali metal alcoholates are preferred where X is an oxymethylene group, sodium methylate being especially preferred, and pulverized alkali hydroxides or potassium carbonate are preferred where X is a carbonyl group, potassium and sodium hydroxides being especially preferred. Although temperature and pressure are not critical, the reaction is preferrably carried out between about 0C and 40C. The epoxide of formula I is thus obtained in a smooth reaction.

The above method, involving the compounds of formula III as a reactant, offers the advantage that, with esters and ethers, only the terminal double bond is epoxidized. By contrast, in making compounds of formula I having more than one double bond from the compounds of formula II, the terminal double bond is not selectively converted into the corresponding epoxide using a peracid. Rather, a mixture of epoxides is generally obtained using a peracid which can be separated in a manner known per se by chromatography.

A further method of preparing compounds of formula I of the instant invention involves reacting the compounds of formula IV with the compounds of formula V. This reaction is generally carried out in any conventional inert organic solvent. Preferred inert organic solvents are benzene, toluene, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, with tetrahydrofuran being especially preferred. To the reaction mixture is added an aprotonic solvent. Any conventional aprotonic solvent can be utilized, but hexamethyl phoscri c Ion ca 2 =cn CH2" CH2 C. In carrying out this reaction, the hydroxyl group on either of the compounds of formula IV or V is initially converted by conventional techniques, in an inert solvent, into an alkali metal salt. One method of converting to the alkali metal salt is by reacting the compound of either formula IV or V, where either I or K is a hydroxyl group with a suitable base such as an alkali metal hydride, e.g. sodium hydride utilizingtetrahydrofuran as a solvent. This alkali metal salt is then reacted with the halide of either compound IV or V to yield compound VI.

A still further method for preparing a compound of formula I of the instant invention involves reacting a carbonyl compound of formula VII with a phosphine oxide of formula VIII to obtain a compound of .formula IX. Although temperature and pressure are not critical, this reaction is preferably effected in a temperature range of 0C. to about 40C. The reaction is carried out in the presence of a base and in an inert solvent. Any conventional base and inert organic solvent can be utilized in this reaction. The preferred bases are, however, the alkali metal hydrides, such as sodium hydride, preferably dissolved in benzene, toluene, dimethylformamide, tetrahydrofuran, dioxane or 1 ,2- dimethoxyethane and the alkali metal alcoholates, such as sodium methylate, preferably dissolved in an alcohol, such as methanol. In a particularly preferred reaction, a compound of formula VII is reacted with a phosphine oxide of formula VIII in the presence of 2 moles of sodium hydride in absolute tetrahydrofuran, excess sodium hydride being decomposed by adding absolute alkanol prior to the working up.

When R and R form an additional carbon to carbon bond in compounds of formula VI or IX, the compounds of formula I can be formed by selective hydrogenation of the acetylenic bond in the compound of formula VI or IX to an olefin double bond. For this purpose, the acetylenically unsaturated compound is dissolved in an inert-solvent, preferably a high-boiling petroleum ether, and is partially hydrogenated in the presence of a partially inactivated catalyst, such as a lead/palladium catalyst deactivated with quinoline; Helv. Chim Acta 35, 446 (1952); Hoppe-Seylers Z. Phsiol. Chem. 295,290 (1935).

The starting materials of formula II, used in the process in accordance with the instant invention, can be obtained according to several procedures. One method of obtaining compounds of formula II wherein X is oxymethylene consists of reacting a compound of the formula:

l l c =CI-i cu-x IV-A m n with a compound of the formula:

wherein R,. R R R R R R R,,, R R m and n about C to about the boiling point of the reaction are as above and one of K and J is a halogen and the mixture. This reaction is also carried out in the presother is an alkali salt of the hydroxy group. ence of an acid binding agent such as pyridine, triethyl This reaction is carried out in the same manner as deamine, quinoline, with pyridine being preferred, to give scribed hereinabove with respect to reacting comthe desired allyl or propargyl ester. The propargyl ester pounds of formula IV with compounds of formula V. can be partially hydrogenated to a compound of for- This reaction can be effected in any conventional inert mula II.

organic solvent, preferably benzene, toluene. dioxane, Starting compounds of formula III are obtained by l,2-dimethoxyethane ortetrahydrofuran. Although the hydroxyhalogenating a compound of formula II. This temperature and pressure ofthe reaction is not critical, l0 hydroxyhalogenation can be carried out by convena temperature range lying between 0C. and the boiling tional procedures. In accordance with a preferred empoint of the solvent concerned is preferred. An aprobodiment of this invention, the compound of formula tonic solvent such as hexamethyl phosphoric acid tri- II is suspended in water and treated with an equal amide is preferably also added to the reaction mixture. amount of an inert organic solvent to form a homoge- One method of obtaining compounds of formula II neous. concentrated solution. Any conventional inert wherein X is oxycarbonyl consists of reacting a comorganic solvent such as tetrahydrofuran, dioxane. 1,2- pound of the formula: dimethoxyethane, etc., preferably tetrahydrofuran can 1 62 3 ca e=cc;-: ca c =cacrl cn l1=o VII-A l l l wherein R R R;,, R and m are as above; with a combe utilized. This solution can be treated with a convenpound of formula VIII. This reaction is carried out in tional hydroxyhalogenating agent to hydroxyhalogenthe same manner as described hereinabove with rex0 ate the compound offormula II. If, for example, acomspect to reacting compounds of formula VII with compound of formula III is desired wherein Z is bromine, pounds of formula VIII. This reaction is expediently N-bromo-succinimide is introduced portionwise into carried out in the presence of a base. preferably dissuch a solution in a temperature range of from about solved in an inert organic solvent. 0C. to 40C. If compounds of formula III are desired Another method for obtaining compounds offormula II wherein X is oxycarbonyl consists of esterifying an wherein Z is chlorine or iodine, N-chloro-succinimide 35 or N-iodo-succinimide is correspondingly used. A preacid of the formula: ferred temperature range for carrying out this reaction l cn c :c Tca ca -c =ca ca cli [c ca coon x I R m 11 wherein R R R R m and n are. as above; with a lies between 0C. and 5C.

compound of formula V wherein I is a hydroxyl group. The compounds of formula I of the instant invention Any of the conventional methods of esterifying an acid exist as a cis/trans isomer mixture. The mixture can, for with an alcohol can be utilized in carrying out this reacexample, be separated into the isomeric forms by adtion. In accordance the a preferred embodiment of this sorption on a material with selective acidity. For examinvention. the acid of formula X is reacted with a halople, isomer mixture can be dissolved in an inert organic gena ing ag n u h s hi nyl hl ri hi nyl r solvent, such as hexane, diethyl ether or acetic acid mide, phosphorous trichloride. phosphorous oxychloethyl ester, and adsorbed on Kieselgel. The isomers adride etc.. with thionyl chloride being preferred. The hab d i diff t zones can be eluted with one of the logenation of the acid of formula X is carried out in the l t or l t mi ture mentioned hereinbefore pr ence f an in rt rg ni l such as petroleum and isolated. The isomer mixture can. in individual etheri benzene, hcxanei Within tempflatufe cases. also be separated by fractional distillation or oplfll'lgC from about 0C 10 about the bOlllIIg pOlIlt Of the tionally preparative thin layer chromatography, reaction mixture. This halogenation reaction is carried Th f llowi g examples illustrate the invention. All out in the presence of an Organic amine base y of temperatures are stated in degrees Centigrade. Nujol is the conventional organic amine bases such as pyridine, i l oil, and the percent of hydride in the mineral triethylamine, quinoline, etc. can be used, but pyridine il suspension is given as percent by weight.

is preferred. The resulting acid halide can then be reacted by conventional means with the compound of EXAMPLE 1 formula V. wherein J is a hydroxy group. to produce 2,4 g of sodium hydride (50% Nujol suspension) is the compound offormula II, wherein X is oxycarbonyl. 63 washed twice with hexane and overlaid with 10 ml Of Generally, this reaction is carried out in an inert orabsolute tetrahydrofuran and, with stirring and iceganic solvent, such as benzene, toluene, hexane. isocooling, 11.9 g of 10,1 l-epoxy-3,7,l l'trimethyl-2- octane. chloroform, carbon tetrachloride or ethylene cis/trans, 6-cis-dodecadien-l-ol in 10 ml of absolute glycol dimethyl ether within a temperature range'from' tetrahydrofuran is added dropwise, and the mixture is further stirred at room temperature for 1 hour. With ice-cooling, 7 g of allyl bromide and 20 ml of hexamethyl phosphoric acid triamide are successively added dropwise, and the mixture is further stirred at 50C. for 3 hours. The cooled reaction mixture is poured onto ice-water and exhaustively extracted with hexane. The combined hexane extracts are worked up by washing with saturated aqueous sodium chloride solution, followed by drying over sodium sulphate and then filtering and evaporating. After working up in the preceding manner, the residues are chromatographed on Kieselgel with hexane and acetic ester (4:1 parts by volume) to yield pure 1-(allyloxy)-10,l l-epoxy-3,7,l ltrimethyl-2-cis/trans, 6-cis-dodecadiene. A sample is distilled in the bulb-tube. Boiling point ca l20/10 mmHg; r1 1.4785.

EXAMPLE 2 A solution of 4.4 g of sodium in 95.5 ml of absolute methanol is added dropwise with ice-cooling to a solution of 73 g of 3-bromo-2,6,10-trimethyl-12-[(trans-3- methyl-2-penten-4-ynyl)-oxy]-6-cis, lO-cis/transdodecadien-Z-ol in 95.5 ml of absolute methanol and the mixture is subsequently further stirred for 0.5 hours. The reaction mixture is poured onto ice-water, exhaustively extracted with diethyl ether and worked up as described in Example 1. By chromatography on Kieselgel with hexane and diethyl ether (4:1 parts by volume), there is obtained pure 10,1 1-epoxy-3,7,l 1- trimethyl-1-[(trans-3-methyl-2-penten-4-ynyl)-oxy]-2- cis/trans, -cis-dodecadiene which decomposes on distillation in high vacuum. A sample is distilled in the bulb-tube; boiling point ca 140l451 l0 mmHgm The starting material is obtained as follows:

39 g of sodium hydride (50% Nujol suspension) is washed twice with hexane and overlaid with 400 ml of tetrahydrofuran, and, with stirring and ice-cooling, 78.2 g of trans-3-methyl-2-penten-4-yn-l-ol is added dropwise, and the mixture is further stirred at room temperature for 1 hour. 232 g of 2-cis/trans, 6- cisfarnesyl bromide and 270 ml of hexamethyl phosphoric acid triamide are subsequently successively added dropwise, and the mixture is stirred at 50 for 3 hours and worked up as described in Example 1. By chromatography on Kieselgel with hexane and diethyl ether (97.5:2.5 parts by volume), there is obtained pure trans-3-methyl-2-penten-4-ynyl 3,7,1 l-trimethyl- 2-cis/trans, 6-cis,l0-dodecatrienyl ether. A sample is distilled in the bulb-tube. Boiling point ca 120-127/0.00l5 mmHg; n 1.5012.

89.3 g of N-bromosuccinimide is added portionwise with ice-cooling to a homogeneous solution of 134 g of trans-3-methyl-2-penten-4-ynyl 3,7,1 l-trimethyl-Z- cis/trans, 6-cis,10-dodecatrienyl ether in 1300 ml of tetrahydrofuran and 208 ml of water. The mixture is further stirred for 4 hours with ice-cooling and worked up as described in Example 1. By chromatography on Kieselgel with hexane and diethyl ether (4:1 parts by volume), there is obtained pure 3-bromo-2,6,l0- trimethyll 2-[(trans-3-methyl-2-penten-4-ynyl )-oxy]- 6-cis-l0-cis/trans-dodecadien-Z-ol which decomposes on distillation in high vacuum. r1 1.5213 (sample dried in high vacuum at 50 for 3 hours).

EXAMPLE 3 0.6 ml of quinoline and 0.6 g of Lindlar catalyst are added to a solution of 6 g of 10,1 1-epoxy-3,7,1 1- trimethyl-l trans-3-methyl-2-penten4-ynyl )-oxy]-2- cis/trans, 6-cis-dodecadiene in 60 ml of petroleum ether (b.p. 80l10C), and the mixture is hydrogenated up to the uptake of the theoretical amount of hydrogen, filtered from the catalyst and evaporated. In order to remove the quinoline, the reaction mixture is worked up by chromatographing on Kieselgel with hexane and diethyl ether (4:1 parts by volume) and a sample distilled in the bulb-tube. There is obtained 10,1 1- epoxy-3,7,1 l-trimethyl-[(trans-3-methyl-2,4-

pentadienyl)-oxy]-2-cis/trans, 6-cis-dodecadiene. Boiling point ca 120"/10 mmHg; n,, 1.4967.

EXAMPLE 4 0.5 ml of quinoline and 0.5 g of Lindlar catalyst are added to a solution of 5 g of l-(propynyloxy)-6,7- epoxy-3,7-dimethyl-2-cis/trans-octene in ml of petroleum ether (b.p. 80-1 10C), and the mixture is hydrogenated up to the uptake of the theoretical amount of hydrogen filtered from the catalyst, evaporated and worked up as described in Example 3. l-(allyloxy)-6,7- epoxy-3,7-dimethyl-2-cis/trans-octene, obtained thereby, boils at /0.08 mmHg; m, 1.4632.

EXAMPLE 5 43.3 g of m-chloroperbenzoic acid are added portionwise with ice-cooling to a solution of 33 g of allyl 3,7-dimethyl-2-cis/trans, 6-octadienyl ether in 350 ml of methylene chloride, and the mixture is further stirred with ice-cooling for 2 hours, subsequentlydiluted with 250 ml of methylene chloride and successively washed with ice-cold l-N-caustic soda and saturated aqueous sodium chloride solution, dried over sodium sulphate, filtered and evaporated. By chromatography on Kieselgel with hexane and diethyl ether (4:1 parts by volume) and subsequent distillation, there is obtained pure l-(allyloxy)-6,7-epoxy-3,7-dimethyl-2- cis/trans-octene; boiling point -72/0.1 mml-lg; n 1.4633.

The starting material is obtained as follows:

48 g of sodium hydride (50% Nujol suspension) is washed twice with hexane and subsequently overlaid with 500 ml of absolute tetrahydrofuran. With stirring and ice-cooling, 58 g of allyl alcohol is added dropwise and the mixture is stirred at room temperature for 1 hour. With ice-cooling, 220 g of 2-cis/transgeranyl bromide and 400 ml of hexamethyl phosphoric acid triamide are successively added dropwise, and the mixture is heated at reflux for 3 hours. The mixture is subsequently worked up as described in Example 1 and fractionally distilled. Boiling point 5 l/0.0 l 5 mmHg; n 1.4695.

EXAMPLE 6 9 g of m-chloroperbenzoic acid (93%) is added portionwise with ice-cooling to 9.3 g of 2-cis/transgeranium acid allyl ester in ml of methylene chloride, and the mixture is further stirred with ice-cooling for 2 hours. The mixture is then worked up by being di luted with 100 ml of methylene chloride, washed initially with ice-cold l-N caustic soda and thereafter with saturated aqueous sodium chloride solution. dried over sodium sulphate, filtered and evaporated. After being worked up in the preceding manner, the residues are chromatographed on Kieselgel with hexane and diethyl ether (4:1 parts by volume) and subsequent distilled to obtain pure 6,7-epoxy-3,7-dimethyl-2- cis/transoctenoic acid allyl ester; boiling point 8l-84/0.05 mml-lg; n,," 1.4728.

The starting material is obtained as follows:

20.2 g of thionyl chloride is added dropwise with icecooling to a solution of 25.2 g of geranium acid and 13.5 g of pyridine in 150 ml of absolute ether, and the mixture is stirred at room temperature for 1 hour with the exclusion of moisture. The precipitated pyridine hydrochloride is rapidly filtered off, rinsed with hexane and the reaction solution evaporated in vacuum. The unpurified geranium acid chloride is taken up in 100 ml of absolute benzene and, with ice-cooling, added dropwise to a solution of 9.3 g of allyl alcohol and 13.5 g of pyridine in 200 ml of hexane and 80 ml of benzene and further stirred at room temperature for 1 hour. The reaction mixture is poured onto ice-cold, dilute hydrochloric acid, the organic phase is separated off, and the aqueous-hydrochloric acid phase is extracted twice with hexane. The combined organic phases are successively washed neutral with saturated aqueous sodium bicarbonate solution and saturated aqueous sodium chloride solution, dried over sodium sulphate, filtered off and evaporated. By chromatography on Kieselgel with hexane and diethyl ether (9:1 parts by volume) and subsequent distillation, there is obtained pure 2- cis/transgeranium acid allyl ester; boiling point 70/0.0lmml-lg; m, 1.4800.

EXAMPLE 7 10.3 g of m-chloroperbenzoic acid is added portionwise with ice-cooling to 12.6 g.of 3,7,1 l-trimethyl-2- cis/trans, 6-trans, lO-dodecatrienoic acid trans-3- methyl-2-penten-4-ynyl ester in 120 ml of methylene chloride. The mixture is further stirred with ice-cooling for 2 hours and worked up and chromatographed as described in Example 6. The pure 10,1 l-epxy-3,7,l ltrimethyl-Z-cis/trans, 6-trans-dodecadienoic acid trans- 3-methyl-2-penten-4-ynyl ester obtained boils in the bulb-tube with decomposition at ca l5O/l0 mmHg; n,, 1.5020.

The starting material is obtained as follows:

24.6 g of 3,7,1 l-trimethyl-Z-cis/trans, 6-trans, l0- dodecatrienoic acid chloride in 70 ml of absolute benzene is added dropwise with ice-cooling to a solution of 9.6 g of trans-3-methyl-2-penten-4-yn-l-ol and 8.15 ml of absolute pyridine in 200 ml of hexane and 55 ml of absolute benzene, further stirred at room temperature for 1 hour and worked up and chromatographed as described in Example 6, second part. Asample of the pure 3,7,1 l-trimethyl-2-cis/trans, 6-trans, l0- dodecatrienoic acid trans-3-methyl-2-penten-4-ynyl ester boils in the bulb-tube at ca 130/l0' mml-lg; n 1.5098.

EXAMPLE 8 11.5 g of m-chloroperbenzoic acid is added portionwise with ice-cooling to 12.5 g of 3,7-dimeth'yl-2,6- octadienyl l,l-dimethyl-2-propenyl ether in 130 ml of methylene chloride. The mixture is stirred for 2 hours, thereafter diluted with 130 ml of methylene chloride and successively washed with ice-cold l-N caustic soda and saturated aqueous sodium chloride solution, dried over sodium sulphate and evaporated. The residue is chromatographed on Kieselgel with hexane and diethyl ether (9:1 parts by volume). There is obtained pure 6,- 7-epoxy-3 ,7-dimethyll l l -dimethyl-2-propenyl oxy]-2-octene. Boiling point 80/O.l5 mml-lg; n 1.4619.

The starting material is obtained as follows:

9.6 g of sodium hydride (50% Nujol suspension) is washed twice with hexane and overlaid-with 80 ml of absolute tetrahydrofuran. With ice-cooling, 17.2 g of 2-methyl-3-buten-2-ol in 150 ml of absolute tetrahydrofuran is added dropwise, and the mixture is stirred EXAMPLE 9 2.5 g of m-chloroperbenzoic acid (93%) is added portionwise with stirring and ice-cooling to 3.8 g of 3,6- ,7-trimethyll -[(oz-vinylpiperonyl )oxy]-2-cis/trans, 6- octadiene in 40 ml of methylene chloride, and the mixture is further stirred with ice-cooling for Zhours. The reactionmixture is subsequently diluted with 40 ml of methylene chloride and washed with ice-cold l-N caustic soda and saturated aqueous sodium chloride solution, dried over sodium sulphate and evaporated. By chromatography on Kieselgel with hexane and diethyl ether (4:1 partsby volume), there is obtained pure 6,7- epoxy-3 ,6,7-trimethyl- 1-[(a-vinylpiperonyl)oxy]-2- cis/trans-octene. A sample boils in the bulb-tube at ca l35/0.00l mml-lgflt 1.5230.

The starting material is obtained as follows:

4.4g of sodium hydride (50% Nujol suspension) is washed with hexane and overlaid with 40 ml of absolute tetrahydrofuran. With ice-cooling, 16 g of a-ethynylpiperonyl alcohol in 120 ml of absolute tetrahydrofuran is'added dropwise, and the mixture is further stirred at room temperature for 1 hour. 21 g of 3 ,6,7-trimethyl-2-cis/trans, 6-'octadienyll -bromide and 40 ml of hexamethyl phosphoric acid triamide are subsequently successively added dropwise with icecooling, and the mixture is stirred at room temperature for 1 hour, poured onto saturated aqueous sodium chloride solution, and exhaustively extracted with diethyl ether. The ether solution is washed with saturated aqueous sodium chloride solution, dried and evaporated. By chromatography on Kieselgel with hexane and diethyl ether (9:1 parts by 'volume), there is obtained pure 3,6,7-trimethyl-l-[a-ethynylpiperonyl)oxyl-2-cis/trans, -octadiene; n 1.5366.

0.7 ml of quinoline and 0.7 g of Lindlar catalyst are added to 6.6 g of 3,6,7-trimethyl-l-[(aethynylpiperonyl)oxy]-2-cis/trans, 6-octadiene in 60 ml of high-boiling petroleum ether-acetic ester (3:1 and the mixture is hydrogenated up to the uptake of the theoretical amount of hydrogen. The reaction solution issubsequently filtered off from the catalyst and successively washed with ice-cold aqueous l-N hydrochloric acid, with aqueous sodium bicarbonate solution and saturated aqueous sodium chloride solution and dried over sodium sulphate and evaporated. By chromatography on Kieselgel with hexane and diethyl ether (:15 parts by volume), there is obtained pure 3,6,7- trirnethyll q-vinylpiperonyU-oxy ]-2-cis/trans, 6- octadiene. A sample boils in the bulb-tube at ca 82/6 mml-lg; n,, 1.4388.

EXAMPLE 10 14.6 g of m-chloroperbenzoic acid (93%) is added portionwise with stirring and ice-cooling to 12 g of allyl 1,5-dimethyl-4-hexenyl ether in 120 ml of methylene chloride, and the mixture is-further stirred with icecooling for 1 hour. The reaction mixture is subsequently diluted with 120 ml of methylene Chloride and washed with ice-cold l-N caustic soda and saturated aqueous sodium chloride solution. dried over sodium sulphate and evaporated. By chromatography on Kieselgel with hexane and diethyl ether (9:1 parts by volume). there is obtained pure 1-(allyloxy)-4,5-epoxy- 1.5-dimethyl-hexane. Boiling point ca 80/0.005 mmHg; 11,, 1.5230.

The starting material is obtained as follows:

9.6 g of sodium hydride (50% Nujol suspension) is washed with hexane and overlaid with 100 ml of absolute tetrahydrofuran. With ice-cooling, 25.4 g of 6-methyl-5-hepten-2-ol is added dropwise, and the mixture is further stirred at room temperature for 1 hour. 24.2 g of allyl bromide and 70 ml of hexamethyl phosphoric acid triamide are subsequently successively added dropwise, and the mixture is stirred at room temperature for 16 hours, poured onto ice-water, exhaustively extracted with diethyl ether, washed with saturated aqueous sodium chloride solution and evaporated. By chromatography on Kieselgel with hexane and diethyl ether (9:1 parts by volume) and subsequent distillation, there is obtained pure allyl 1,5-dimethyl-4- hexenyl ether. Boiling point 63-64/7 mmHg; 1.4442.

EXAMPLE 11 To a solution of 5.8 g 1-(propynyloxy)-l0,1l-epoxy- 3,7,l0,11-tetramethy1-2,6-dodecadiene (cis and transmixture) in 60 ml of high-boiling petroleum ether is added 0.6 ml of quinoline and 0.6 g of Lindlar catalyst. The mixture is hydrogenated up to the uptake of the theoretical amount of hydrogen, filtered to remove the catalyst, and then evaporated to dryness. In order to remove the quinoline, the reaction mixture is chromatographed on Kieselgel with hexane and diethyl ether (4:1 parts by volume) and distilled. There is obtained 1-(a11y1oxy)-10, 1 1-epoxy-3,7,10,1 1-tetramethy1-2,6- dodecadiene (cis and trans-mixture). Boiling point 1 l-116C/0.035 mml-lg; n 1.4779.

EXAMPLE 12 To a mixture of g 3-bromo-2,6,IO-trimethyl-l2- allyloxy-6,10-dodecadien-Z-ol (cis and trans-mixture) in 14 ml absolute methanol is added dropwise, with icecooling, a solution of 645 mg sodium in 14 ml absolute methanol and the mixture is subsequently further stirred for 1 hour. The reaction mixture is poured onto ice-water, exhaustively extracted with diethyl ether, and worked up as described in Example I. By chromatography on Kieselgel with hexane and diethyl ether (4:1 parts by volume), there is obtained pure 1- (allyloxy)-10,1 l-epoxy3,7,l 1-trimethy1-2.6- dodecadiene (cis and trans-mixture). Boiling point 99l00C/0.002 mmHg; n 1.4751.

The starting material is obtained as follows:

4.8 g of sodium hydride (50% Nujol suspension) is washed twice with hexane andoverlaid with 57 ml of absolute tetrahydrofuran. With stirring and ice-cooling, 5.8 g allyl alcohol is added dropwise, and the mixture is further stirred at room temperature for -1 hour. 28.5 g farnesyl bromide (cis and trans-mixture) and 40 ml hexamethyl-phosphoric acid-triamide are subsequently, successively added dropwise, and the mixture is stirred at room temperature for 2 hours and worked up as described in Example 1. By chromatography on Kieselgel with hexane and diethyl ether (9:1 parts by volume) is obtained pure al1yl-(3,7,l l-trimethyl- 2,6,10-dodecatienyl)-ether (cis and trans-mixture). Boiling point 9495C/.00l mmHg; fl 14807.

'To a homogeneous solution of 14.5 g allyl-(3.7.l ltrimcthyl-2,6,l0-dodecatrienyl)-ether (cis and trans mixture) in 155 ml tetrahydrofuran and 25 ml water is added portionwise with ice-cooling 12.4 g N- bromosuccipimide. The mixture is further stirred under ice-cooling -for 6 hours and worked up as described in Example 1. By chromatography on Kieselgel with hexane and diethyl ether (4:1 parts by volume) is obtained pure 3-bromo-2,6, l O-trimethyl-l 2-a1lyloxy-6,10- dodecadiene-2-ol (cis and trans-mixture). mf 1.5022.

EXAMPLE 13 A solution of 650 mg sodium in 16 ml absolute methanol is added dropwise with ice-cooling to a solution of 9.33 g 4-bromo-3,7,l 1-trimethy1-l3-allyloxy-7,l 1- tridecadien-3-ol (cis and transmixture) in 16 ml absolute methanol, and the mixture is subsequently further stirred for 1 hour. The reaction mixture is poured onto ice-water, exhaustively extracted with diethyl ether and worked up as described in Example 1. By chromatography on Kieselgel with hexane and diethyl ether (4:1 parts by volume), there is obtained pure 1-(allyloxy)- 10,1 1-epoxy-3,7,1 1-trimethyl-2,6-tridecadiene (cis and trans-mixture). Boiling point ca C/.005 mmHg; (bulb-tube). n 1.4768.

The starting material is obtained as follows:

4.5 g sodium-hydride (50% Nujol suspension) is washed twice with hexane and overlaid with 17 m1 of absolute tetrahydrofuran. With stirring and cooling, 20.2 g 3,7,1 l-trimethyl-2,6.IO-tridecatriene-l-ol (cis and trans-mixture) is added dropwise, and the mixture is further stirred for 1 hour at room temperature. 10.9 g allylbromide and 34 ml hexamethyl phosphoric acid triamide are subsequently. successively added dropwise, and the mixture is further stirred at room temperature for 16 hours and worked up as described in Example 1. By chromatography on Kieselgel with hexane and diethyl ether (4:1 parts by volume) is obtained pure ally1-(3,7,1 1-trimethyl-2,6,lO-tridecatrienyl)- ether (cis and transmixture). Boiling point 87C/.001 mml-lg; r1 1.4813.

8.9 g N-bromosuccinimide is added portionwise with ice-cooling to a homogeneous solution of 13.8 g allyl- (3,7,1 1-trimethyl-2,6,l0-tridecatrienyl)-ether (cis and trans-mixture) in m1 tetrahydrofuran and 23 ml water. The mixture is further stirred with ice-cooling for 6 hours and worked up as described in Example 1. By chromatography on Kiesclgel with hexane and diethyl ether (4:1 parts by volume), there is obtained pure 4-bromo-3,7,l l-trimethyl- 1 3-a1lyloxy-7,l ltridecadiene-3-ol (cis and trans-mixture). 1.5035.

EXAMPLE 14 A solution of 350 mg sodium in 8.5 ml absolute methanol is added dropwise with ice-cooling to a solution of 5.08 g 4-bromo-7-ethyl'3,l l-dimethyl-l3-allyloxy- 7,1 l-tridecadien-3-ol (cis and trans-mixture) in 8.5 ml absolute methanol. The mixture is subsequently, further stirred for 1 hour. poured onto ice-water. exhaustively extracted with diethyl ether worked up as described in Example 1. By chromatography on Kieselgel with hexane and diethyl ether (4:1 parts by volume), there is obtained pure ethyl-3,11-dimethyl-2,6-tridecadiene (cis and transmixture). Boiling point ca 125C/.001 mmHg; r1 1.4772.

The starting material is obtained as follows:

2.44 g sodium hydride (50% Nujol suspension) is washed twice with hexane and overlaid with 11 ml absolute tetrahydrofuran. With stirring and ice-cooling, a solution of 12.7 g 7-ethyl-3,11-dimethyl-2,6,10- tridecatrien-l-ol (cis and trans-mixture) in 11 ml absolute tetrahydrofuran is added dropwise, and the mixture is further stirred at room temperature for 1 hour.- 6.5 g allylbromide and 20 ml hexamethylphosphoric acid triamide are subsequently successively added dropwise, and the mixture is stirred at room temperature for 4 hours and worked up as described in Example 1. By chromatography on Kieselgel with hexane and diethyl ether (4:1 parts by volume), there is obtained pure al1yl-(7-ethyl-3,l l-dimethyl-2,6,10- tridecatrienyl)-ether (cis and trans-mixture). Boiling point 93C/.001 mmHg; n 1.4800.

5.2 g N-bromosuccinimide is added portionwise with ice-coo1ing to a homogeneous solution of 8.34 g allyl- (7-ethy1-3,1 1-dimethy1-2,6,10-tridecatrieny1)-ether (cis and trans-mixture) in 82 ml tetrahydrofuran and 13 ml water. The mixture is further stirred under icecooling for 6 hours and worked up as described in Example By chromatography on Kieselgel with hexane and diethyl ether (4:1 parts by volume), there is obtained pure 4-bromo-7-ethyl-3,l 1-dimethy1-13- allyloxy-7,1 1-tridecadiene-3-ol (cis and trans-mixture). n 1.5019

EXAMPLE Roundels (10 cm of cotton material are drenched with an acetonic solution of the active, allyl substances of the instant invention and carefully dried. For each substance and concentration, 30-60 freshly laid eggs of the Ephestia Kuhniella are placed on the roundels and brought to hatching in a small cage of plastic at 25C. and high humidity.

The action of the substances manifests itself in the premature or retarded death of the embryos in the egg or upon hatching. The results are expressed in egg morality. The dosage is stated in: 10 g of active substance/cm of cotton material. Thus, dosage 3 meansl-(allyloxy)-10,11-epoxy-7- 10 g/crn Substance Concn. Egg

10 act. mortality substlcm in (dosage) 1-(allyloxy)-6,7- 3 100 epoxy-3 ,7-dimethy1- 4 100 2-octene 6,7-epoxy-3,7- 3 100 dimethy1-2-cis/trans' 4 100 octenoic acid allyl ester 5 100 An acetonic solution of the active substance of the instant invention of known concentration is applied to the abdomen (ventral) of Tenebrio molitor pupae. The treated pupae are left at room temperature for 10 days in Petri dishes and thereafter examined as to whether adult animals have developed from the pupae. The activity of the active substance is stated in percent inhibition of the development of adult animals (AFl) (at the stated concentration).

Substance Concn. g act. AFI subst./pupa in l-(allyloxy)-10,l l- 10* epoxy-3,7,1 l-trimcthyl- 10 100 Z-eis/trans, 6-cis- 10 100 dodecadiene 5X10 100 2 10- 6O 10' 15 EXAMPLE 17 To 13.3 g. of 10,1 l-ep0xy-3,7,10,11-tetramethyl-2,6- dodecadienoic acid dissolved in 200 ml. of pyridine is added 19 g. of p-toluenesulfonic acid chloride. With ice cooling, 9.6 g. of 3-methyl-pent-1-yn-4-en-3-ol is added to the mixture, which is subsequently heated for 5 hours to 40C. The reaction mixture is poured on to water and extracted with diethyl ether, and the extract is washed several times with water. Thereafter, the ether extract is dried over sodium sulfate and evaporated. 5

The crude (3-methyl-pent-1-yn-4-en-yl)-l0,1lepoxy-3,7,10,1 1-tetramethyl-2,6-dienoate obtained is purified by chromatography using 500 g. silica gel. A first fraction is eluted with n-hexane and discarded. The product is eluted with a mixture of diethyl ether/nhexane (1:4 parts by volume), as a pale yellow oil, 1111 1.4860. 

1. 1-(ALLYLOXY)-4-5-EPOXY-1,5-DIMETHYLHEXANE. 